A new NMR technique has been developed that facilitates structure determination and spectral assignment. The method has been used for complete structure determination and spectral assignment of the capsular polysaccharide from E. coli, capsule type 53. Complete 1H and 13C spectral assignment of a large number of polycyclic aromatic compounds has also been obtained with the new method. Improvements for a number of other one- and two-dimensional experiments have been developed. A modification of the solid-state cross-polarization NMR experiment facilitates the application of this technique to nuclei with a very low magnetogyric ratio. A simple modification of the two-dimensional (2D) heteronuclear shift correlation experiment enables spectra to be recorded in the pure absorption mode, improving both sensitivity and resolution. A new one-dimensional technique has been developed that is superior in sensitivity to 2D experiments if only a small number of heteronuclear correlations have to be investigated.